Azo-dyestuffs and process of making same



Patented Mar. 13, 1934 UNITED STATES PATENT OFFICE AZO-DYESTUFFS AND PROCESS OF MAKING SAME No Drawing. Application November 9, 1932,

Serial No. 641,933. 13, 1931 28 Claims.

The present invention relates to the manufacture of new azo-dyestufis. It comprises the process of making these azo-dyestuffs and the azo-dyestufis themselves.

The arylides deriving, on the one part, from carboxylic acids the COOH-groups of which are directly linked to a ring, and which, due to the presence of a COCl-lz-group, are capable of coupling (as in the case of the carboxylic acids of l-aryl-pyrazolones containing their carboxylic group bound, be it to the aryl nucleus, be it to the pyrazolone nucleus, or to both nuclei), and, on the other part, from polynucleal aromatic amines, have not hitherto been described. These arylides correspond to the general formula wherein R1 is the radical of the carboxylic acid containing the group COCHZ, and R2 theradical of the polynuclear amine.

It has now been found that these arylides are obtained by condensing the carboxylic acids with the polynuclear aromatic amines defined below This condensation is preferably eiiected according to known methods, for example by converting the carboxylic acids into the corresponding carboxylic acid chlorides, and condensing the chlorides thus obtained with the polynuclear aromatic amines. The condensation may also be effected by causing condensing agents, such as the trichloride or oxychloride of phosphorus etc., to react on a mixture of the carboxylic acid and the aromatic amine in an indifierent solvent, such as toluene, chlorobenzene, or a tertiary base, such as pyridine, dimethylaniline or diethylaniline.

These new arylides are of great industrial importance.

Among the carboxylic acids which come into consideration for carrying out the present process the following may be mentioned: a

l. The pyrazolone carboxylic acids which are derived from acetoacetic esters and the hydrazines obtained in known manner from aminocarboxylic acids, such as the 1-aminobenzene-2-, or 3- or 4- carboxylic acids, as well as from the different chloroand methylarninobenzoic acids, such as for example 5 chloro 2 aminobenzene-l-carboxylic acid, 2 chloro 3 aminobenzene-l-carboxylic acid, 4-ch1oro-3-arninobenzene-l-carboxylic acid, 5-chloro-3-aminobenzene-l-carboxylic acid, 6-chloro-3-aminobenzene-l-carboxylic acid, 2-ch1oro-4=-aminobenzene-l-carhoXylic acid, or 2- methyl 4 aminobenzene-l-carboxylic acid, 2- methyl 6 aminobenzene-l-carboxylic acid, lmethyl 2 aminobenzene-l-carboxylic acid, i-

In Switzerland November methyl 3 aminobenzene-l-carboxylic acid, as well as from the chlorotoluidine carboxylic acids,

such as, for examples, 6-chloro-4-methyl-3- aminobenzene l carhoxylic acid, 5-chloro-4- methyl 2 aininohenzene-l-carboxylic acid, as well as from the alkyl, aralkyl, and aryl ethers of aininophenol carboxylic acids, such as, for

example, S-arninoi-methoxy-l-carboxylic acid, the phenyl ether of 2-amino-l-hydroxybenzenel-carboxylic acid, or the substitution products thereof, etc. i

2. The pyrazolone carboxylic acids which are derived from oxalacetic esters and the hydrazines corresponding to the general formula group in the aromatic nuceli, acids of the type of the benzoylacetic-ortho-carboxy1ic acid, etc.

Among the pclynuclear amines which come into question as parent materials for the present invention there may be named the amines the nuceli of which are purely aromatic, such as a-.

and s-naphthylamine, the naphthylenediamines, for example 1:5-naphthylenediamine, the aminonaphthols, the Z-aminoanthracene and 1- aminoacenaphthene, etc., i. e., polynuclear amines whose nuceli are condensed the one with the other, or polynuclear amines whose nuclei are united by a linkage consisting either of a simple link or an atom or a grouping of atoms. Among the polynuclear amines whose nuclei are united by a simple link there may be named the 4:4- diaminodiphenyls, such as benzidine, tolidine, dianisidine, diphenetidine. Among the polynuclear amines whose nuclei are united by an atom or a grouping of atoms there may be named the diphenylethers containing one or several NEE-groups, such as the Z-amino-l:l'-diphenylother or the a:4-diamino-1:l-diphenylether, l

acids, pyrazolone carboxylic acids, the aminoazocompounds, aminothiazines, oxazines, azines, etc. Other amino compounds may. also be used, for example the condensation products containing amino groups which are inter alia obtained by condensation of aromatic diamines with heterocyclic. compounds containing mobile halogen atoms, such as cyanuric chloride, dichloroquinazol'ine, tribromopyrimidine, etc., products which asis known may contain a great number of NH2- 1 groups. 1

According to the i0 pics of the initial products mentioned above arylides of different constitution are obtained.

Thus the arylides which are obtained from 5- pyrazolone carboxylic acids correspond to the general formula R1--CONHR2 cited in the third paragraph above, wherein R1 stands for the radical of the pyrazolone carboxylic acid, it being indifferent whether the carboxyl group is in the pyrazolone nucleus or, if one is present, in the phenyl nucleus, and R2 for the residue of the polyriuclear amine.

According to thetnature of the pyrazolone carboxylic acid furthei more specific formulas may be derived from th s general formula. Thus the arylides from pyra olone carboxylic acids mentioned under position 1 above correspond to the following general formula deriving from that of the third paragraph hereinbefore wherein R1 stands for the aromatic radical of the aromatic carboxylic acid used for the production of the pyr zolone, and R2 for the radical of the polynuclear aromatic amine.

The arylides which derive from the pyrazolone carboxylic' acidsmentioned under position 2 above correspond'tothe following particular case of the general formula disclosed in the third paragraph above, wherein or aryl, and R2 for the radical of the polynuclear aromatic amine, and in which the grouping corresponds to the radical R1 of the general formula stated in the third paragraph.

If one of the acids mentioned under position 3 above is used, the formula of the third paragraph of this specification assumes the following aspect wherein A stands for the radical which contains the CO-CH2-group capable of coupling, R3 for the aromatic nucleus to which the group A and the C0NHR2-group are linked, and R2 for the radical of the polynuclear aromatic amine.

If for the polynuclear aromatic amine such an amine is chosen which contains two or more amino-groups, there are obtained products for which the formula of the third paragraph of this description has developed to the following formula wherein R1 again stands for the radical of the cyclic carboxylic acid carrying the CH2CO- group, and R2 for the radical of the polynuclear aromatic amine, and in which n stands for a whole number which corresponds to the number of MHz-groups which are present in the polynuclear amine.

All these arylides have the common characteristic of being soluble in caustic alkalies and capable of coupling with diazo-compounds. They constitute in a dry state colorless to lightly colored powders.

According to their composition the new arylides may be used for the most various purposes. In a general manner they yield soluble dyestuffs when coupled with sulfcnated diazo components. These dyestuffs may be used for the dyeing of animal fibers (wool and silk), vegetable fibers (cotton, linen, jute etc.), or artificial fibers (artificial silk produced on the basis of regenerated cellulose). If the diazo components contain an OH- group or a COOH-group in ortho position to the diazo-group, there are obtained dyestuffs capable of being transformed in substance, in the dyeing bath, or on the fiber, into metalliferous compounds which dye the fiber shades of excellent fastness properties.

These new dyestuifs correspond to the general formula wherein R1 and R2 have the above stated significations, and R4 stands for the aromatic radical of the diazotizing component. According to the nature of the arylide used for coupling, various special cases may be derived from this general formula, of which the most important are the following:

m stands for hydrogen or a substituent from a group of substituents. comprising alkyl, aralkyl,

in which formulas R4 always stands for the aro matic radical of the'diazo component, R1 for the l the different fibers.

radical of the cyclic carboxylic acid carrying the CH2-CO-group, R for the radical of the polynuclear amine, A for the radical containing the CHz-COz-group capable of coupling, R3 for the aromatic nucleus to which the groups A and CO NH-R2 are linked, :c for H or a substituent from a group of substituents comprising alkyl, aralkyl, or aryl, and n for a whole number which corresponds to the number of NI-Iz-groups present in the polynuclear aromatic amine, if such an amine has been used for the production of the arylide.

All these dyestuiis, indifferent whether they are sulfonated or unsulfonated, or whether or not they contain complexly bound metals, constitute in a dry, finely subdivided state yellow to orange to brown to red powders which dissolve in solvents of the group of solvents comprising water and organic solvents to yellow to orange to brown to red solutions. The dyeings produced with these dyestuffs on textiles range from greenish yellow via golden yellow up to orange, red-orange, brown and red. Many of these dyeings, as already mentioned, are characterized by remarkable fastness properties.

In case these new dyestuffs are metalliferous, the metal may be copper or chromium. But also other metals, such as iron, manganese, nickel, cobalt, molybdenum, cerium, etc., come into consideration, that is to say, all metals the oxides or hydroxides of which may combine with dyestufls to complex compounds.

The arylides obtained according to the process of the present invention vary in their afiinity for In general those which have been prepared with monamines are distinguished by their aiiinity for the animal fiber, whereas those which have been obtained by means of diamines are distinguished by their afiinity for the vegetable fiber or the fiber from regenerated cellulose. Those among the latter which have been obtained with diamines having a pronounced affinity for cotton, such as benzidine, tolidine, dianisidine, etc., are particularly valuable. If the fibers prepared with these arylides are treated with diazotized, preferably unsulionated, amines, there are obtained shades which are remarkable both for their beauty and their fastness.

The following examples illustrate the present invention without, however, limiting the same, the Examples 1 to l illustrating the production of the coupling components necessary for the present invention. The parts are by weight.

Example I A stirring vessel containing a mixture of 200 parts of diethylaniline and parts of pyridine is charged with 24 parts of 1-(3-carboxy-phenyl)-3-methyl-5-pyrazolone and 14 parts of [inaphthylamine; the mixture is heated to about 50 C. and there are gradually added 8 parts of phosphorus trichloride. The temperature is raised to about ISO-140 C. and kept at this point for about 23 hours. The mass is then introduced into dilute hydrochloric acid and the whole is subsequently filtered by suction; the solid matter is suspended in a dilute sodium carbonate solution, the adherent tertiary base is expelled by steam distillation, the arylide is dissolved in a dilute sodium hydroxide solution, and precipitated by the addition of dilute acid after the solution has been clarified. The arylide thus obtained constitutes when dried a whitish powder which is easily soluble in aqueous solutions of caustic alkalies; it is absorbed by cotton, particularly in the presence of electrolytes. The new product very probably corresponds to the formula One proceeds in an analogous manner with other carboxylic acids, such as, for instance, with li carboxy-phenyl) -3-methyl-5pyrazo lone, or by using instead of s-naphthylamine an aminonaphthol, such as, for instance, the 2:7-

or the lz'l-aminonaphthol, or also the dehydrothiotoluidine sulfonic acid.

If pyrazolones are used which are derived from the cxalacetic ester, other stoichiometric proportions must of course be chosen. The same is the case by using instead of pyrazolone other carboxylic acids, such as for example the arylide obtained by condensation of acetylacetic acid and meta-aminobenzoic acid.

Example 2 A stirring vessel is charged with 48.8 parts of l-phenyl-5-pyrazolone-3-carboxylic acid, 43.9 parts of the phenylether of 4-chloro2-aminophenol, and 300 parts of chlorobenzene. The mixture is heated to 130-135 C., allowed to cool down to about 70 (3., and there are added within 30 minutes dropwise 12 parts of phosphorus trichloride. The temperature is again raised to 130-135 C. and maintained at this point for 20 hours. The mass is then poured into water, 5 parts of sodium carbonate added to the mixture, and the chlorobenzene expelled by steam distillation. The solid matter is dissolved in dilute sodium hydroxide solution while hot, filtered, and precipitated by the addition of dilute acid. The new condensation product thus obtained is, when dry, 2. feebly colored powder, which readily dissolves in caustic alkalies. Very fast dyeings are obtained by impregnating wool with its caustic alkali solutions and developing it in suitable diazotizing solutions. The new product probably corresponds to the formula orlz'l-aminonaphthol- If diamines are used, such as'benzidine or 1:5-naphthylenediamine, the stoichiometric proportions may be varied according to the purpose aimed at (condensation with 1 or with 2 amino groups).

Example 3 A stirring vessel is charged with parts of diethylaniline, 44 parts of 1(3-carboxy-phenyl) -3-methyl-5-pyrazolone and 18.4 parts of benzidine. This mixture is heated to about 100 C; and 13.5 parts of phosphorus trichloride are then slowly added, whilst ensuring that the temperature doesnot rise above 110-115 C. This temperature is maintained for about 4 hours, whereupon the mass of the reaction is introduced into dilute hydrochloric acid, and filtered by suction. The solid matter is suspended in dilute sodium carbonate solution, the adherent diethylaniline is expelled by steam distillation, the arylide is dissolved in dilute sodium hydroxide solution and precipitated by the addition of dilute acid after the solution has been clarified. The new product very probably corresponds to the formula t t G The arylide thus obtained constitutes when dried a yellowish powder which is easily soluble in caustic alkalies; it is absorbed by cotton from its caustic alkali solutions, particularly in the presence of electrolytes.

The condensation may be conducted in an analogous manner with other tertiary bases, such as pyridine, or with the use of indifferent solvents, such as, among others, toluene.

Other products having valuable tinctorial properties are obtained by using intead of the 1-(3- carboxy-phenyl) -3-methyl-5-pyrazolone another carboxylic acid, such as 1-(4-carboxy-phenyl)- 3-methyl5-pyrazolone, or the arylide from benzoylacetic ester and para-aminobenzoic acid, or by using instead of benzidine another diamine,

such as a phenylenediamine, dianisidine, tolidine, 1 :5-naphthylenediamine etc.

Example 4 In a mixing vessel provided with a reflux condenser a mixture of 11.2 parts of 1-phenyl-5-pyrazolone-3-carboxylic acid, and 5.4 parts of para-phenylenediamine in 80 parts of pyridine and 120 parts of diethylamine are heated to 100 C. The whole is allowed to cool down to 80 C., and 2.3 parts of phosphorus trichloride are added in the course of 30 minutes. The temperature is maintained at 80 C. for about 30,

minutes, whereupon a further 11.2 parts of 1- phenyl-5-pyrazolone-3-carboxylic acid are added, and the temperature raised to 120-125 C. The

condensation, takes place in the course of 4 hours at 120-125 C., While gradually adding 3 parts of P013. The working up is effected in a similar manner as described in the preceding examples. The new product very probably corresponds to the Other condensation products may be obtained by replacing the para-phenylenediamine by other diamines, such as for example 1:5-naphthylenediamine, 4:4'-diaminodiphenyl ether, 4:4'-di amino-diphenylmethane, etc., as well as by replacing the 1-phenyl-5-pyrazolone-3-carboxylic' acid by other pyrazolone carboxylic acids, or substituted pyrazolone carboxylic acids. By using two different pyrazolone carboxylic acids unsymmetrical condensation products may be obtained.

Example 5 Cotton yarn is impregnated with a grounding solution prepared by dissolving 6 grams of the condensation product from 1 molecular proportion of 1-(4-carboxy-phenyl) -3methyl-5-pyrazclone and 1 molecular proportion of fl-naphthylamine in 300 cc of hot water, with the addition of 12 cc. of sodium hydroxide solution of 30 per cent. strength, 10 cc. of Turkey red oil and 15 grams of sodium chloride, the whole being made up to 1 liter by dilution with water. The goods are wound off and developed in a solution, neutralized by means of sodium acetate, containing per liter the diazo-compound from 3 grams of 1-amino-6-methoxy-4-nitrobenzene. The cotton is dyed a pure red-orange having excellent properties of fastness. The new dyestufi' very probably corresponds to the formula Ewample 6 Cotton yarn is impregnated with a grounding solution prepared by dissolving 6 grams of the condensation product obtained from 1 molecular proportion of 1-(4=-carboxyl-phenyl) -3-methyl- 5-pyrazolone and 1 molecular proportion of 2:7-

amino-naphthol in 300 cc. of hot water, with the azobenzene. A pure yellow dyeing is thus obaddition of 12 cc of sodium hydroxide solution of tained having very good fastness properties. 30 per cent. strength, 10 cc. of Turkey red oil, and The new dyestuif very probably corresponds to 15 grams of sodium chloride, the whole being the formula made up to 1 liter by dilution with water. The O1 goods are Wound off and developed in a solution, H o

neutralized with sodium acetate, containing per O g liter the diazo-compound from 3 grams of 2- amino-4-chlorodiphenylether. The cotton is I )Q dyed an orange having excellent properties of o=N fastness. The new dyestufi very probably cor- (3:0

responds to the formula l H Cotton yarn is impregnated with a grounding I solution prepared by dissolving 6 grams of the condensation product from 2 molecular propor- N tions of 1-(3'-carboxy-phenyl)-3methyl-5-pyrazolone and 1 molecular proportion of benzidine in 300 cc. of hot water, with the addition of 12 cc. of sodium hydroxide solution of 30 per cent. strength, 10 cc. of Turkey red oil, and 15 grams of common salt, the whole being made up to 1 liter by dilution with water. The goods are OH wound off and developed in a solution, neutralized by means of sodium acetate, containing per liter the diazo compound from 3 grams of Jr-chloraminodiphenylether. The cotton is dyed a pure yellow having excellent properties of fastness. The new clyestuff very probably corresponds to Wool yarn is treated for hour at ordinary the formula Example 7 H I H O H H O temperature with a grounding solution containing in respect to the weight of the wool:

3 per cent. of the condensation product obtained according to Example 2 from l-phenyl-5- pyrazolone-3-carboxy1ic acid and 4-chloro-2- aminodiphenylether, 10 per cent. of Turkey red oil, 15 per cent. of sodium hydroxide solution of 36 B., and per liter of the bath 20 cc. of sulfite cellulose waste liquor, and 20 grams of calcined Example 9 The material to be printed is padded in the Foulard apparatus in an alkaline solution con- 1 taining per liter 15 grams of the condensation product from 2 molecular proportions of 1-(3'- carboxy-phenyl)-3-methyl-5-pyrazolone and 1 molecular proportion of para-phenylenediamine. After drying, the goods are printed with a print- Glaubers salt, the ratio of material to liquor ing color containing per kilo 10 grams of the being 1:30. After grounding the goods are hydiazo-product of 2:5-dichloraniline. The yellow droextracted and developed in the course of 20 color develops rapidly and is very fast. The new minutes in a diazo-solution, neutralized by means dyestuff corresponds very probably to the formula c1 01 H t l i -N=N-C|}C\ /CC-N= l r0 l 51 C H3OO=N N=G-CH: O=C|l (|]=0 of sodium acetate, containing in respect to the The production of fast tints on the fiber in weight of the wood 2 per cent. of ortho-chlordiaccordance with the Examples 5 to 9 may further .be carried out with the following diazotizing I bases :1 -a1nino-4-methoxy-2 -nitrobenzene, amino 3 g4-dimethyl-6-chlorobenzene, l-aminoether 2 methyll-methoxy 3:5-dichlorobenzene, 1 amino 2:3:5 trimethyl-ei chlorobenzene, l amino 2:5-dimethy1-4-ohlorobenzene, l-amino- 3:5-dimethyl-6chlorobenzene, l-amino 6 methoxy-3 l-dichlorobenzene, l-arnino-G-methyl- 2 :4 dichlorobenzene, l-amino-Z14:5-trichlorobenzene, 1 amino -2:4:5 -trimethyl 3 chlorobenzene, ortho-aminobenzophenone, 3 aminodiphenylsulfone, the methyl or ethyl esters of the l-aminobenzene-Z-carboxylic acid, the methyl or ethyl esters of 1-amino4i-chlorobenzene-2- amino-5-nitrobenzene-2-carboxylic acid, the

methyl and ethyl esters of I-amino-Z-methoxybenzene-B-carboxylic acid, the anilide of l-arnino 2 methoxybenzene-5-carboxylic acid, the methylor ethyl esters of the phenylether of 2-amino-1-hydroxybenzene-4-carboxylic acid, the 4- chlorophenylether of 2 amino-l-hydroxybenzene i-carboxylic acid, the 2-5-dichlorophenylof 2 amino -'hydroxybenzene-4-carboxylic acid, the phenylether of 2-amino-5-chloro- 1-hydroxybenzenei-carboxylic acid, the anilide of the phenylether of 2-amino-5-chloro-1-hyn I O H droxybenzene-4-carboxylic acid, 1- or 2-aminonaphthalene, l-aminoanthraquinone, etc.

These dyestuifs mayof course also be used as colored lacquers and pigments.

There may here also be mentioned the metalliferous dyestuffs obtained by uniting the coupling components mentioned in the preceding examples with unsulfonated diam-compounds, but contain ing in ortho-position to the'diazo-group an OH- or COOI-I-group, and subsequent treatment with agents capable of yielding metals (of. the French Patent 632,706 and its additional Patents 38,707,

38,749, and 39,207). All these unsulfonated dyestuffs'may be used in the dyeing of lacquers and nitrocellulose varnishes, or varnishes having as basis other products, such as natural or artificial resins.

Example 34.6 parts of sulfanilic acid are diazotizedin known manner and the excess of mineral acid is" neutralized with sodium acetate. The diazosolution is then introduced into a solution, to which has been added sodium bicarbonate, of 50.8 parts of the condensation product from 1 molecular proportion of .para-phenylenediamine and 2 molecular proportions of 1-(3-carboxy phenyl) -3-methyl-5-pyrazolone, which was itself dissolved with the aid of 8 parts of sodium hydroxide.

After some time the dyestufi which has been formed is separated by filtration. pulverized state it constitutes a yellow powder which dissolves in water to a yellow solution. It dyes the fiberyellow shades. On cotton the fastness to light of its dyeings is very good.

By replacing in this example the coupling component by that obtained by condensing 2 mcl of (S-carboxy) -phenylbarbituric acid with 1 mol of benzidine, a similar dyestuff is obtained. The new dyestuif has very probably the formula 0 o H H i"? f? I T=NCH C=O 0:0 HCN=N CONH HNCO o H H o 'ca'rboxylic acid, the methyl or ethyl esters of 1- Example 11 21.7 parts of 4-sulfo-l-aminobenzene-Z-carboxylic acid are diazotized in known manner and the excess of mineral acid is neutralized with sodium acetate. The diazotized mass is introduced into a solution, made alkaline with sodium carbonate, of 29.7 parts of the condensation product from 1 molecular proportion of benzidine and 2 molecular proportions of 1-(3'-carboxyphenyl) -3-methyl-5-pyrazolone.

The dyestuif thus formed is isolated. It very probably corresponds to the formula When dry it is a yellow powder, which in the form of its sodium salt is soluble in water and dyes cotton green-yellow, fast tints which, when treated with agents yielding metal, such as copper salts, are excellently fast to light and washmg.

If in this example there are used instead of 4-sulfo-1-aminobenzene-2-carboxylic acid the sulfaminosalicylic acid or another ortho-aminophenol-sulfonic acid, or l-amino-2-hydroxynaphthanei-sulfonic acid, there are obtained dyestufis which dye cotton fast orange to red and brown tints, the fastness of which in respect of washing and light may be essentially improved by treatment with agents yielding metals, such as copper salts.

Very interesting dyestuffs are also obtained by replacing the copper by other suitable metals, suchas' chromium, nickel, cobalt, cerium, vanadium, manganese, etc. These dyestuffs are particularly valuable when isolated in the form of inetalliferous dyestuifs. Among these there come into consideration the red chromiferous dyestuffs from pyrazolone derivatives, and the yellow chromiferous dyestuffs from the barbituric acid derivatives or of the arylides of acetylacetic acid.

What we claim is:-

1. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula stuffs, consisting in coupling the arylides of the general formula in which R1 stands for the radical of a 5-pyrazolone carboxylic acid, and in which R2 stands for l I I I H2: 0 II the radical of a polycyclic aromatic amine, with aromatic diazo-compounds.

3. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula gether by a linkage, with aromatic diazo-compounds.

5. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula R1CONH-R2 in which R1 stands for the radical of a l-phenyl- 5-pyrazolone carboxylic acid the COOH-group of which is in the phenyl nucleus, and in which R2 stands for the radical of such an aromatic amine which contains two aromatic nuclei bound together by a linkage, with aromatic diazocompounds.

6. Process for the manufacture of azo-dyestuifs, consisting in coupling the arylides of the general formula wherein m stands for hydrogen or a substituent of the group consisting of CH3, OCHs and OCzH, with aromatic diazo-compounds.

7. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula CC=H2 I II H 0 wherein 0: stands for hydrogen or a substituent of the group consisting of CH3, OCHs and OC2H5, with aromatic diazo-compounds.

8. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula in which R1 stands for the radical of a 5-pyrazolone carboxylic acid, and in which R2 stands for the radical of such an aromatic amine which contains two aromatic nuclei bound together by a linkage, with aromatic diazo-compounds.

4. Process for the manufacture of azodyestuifs, consisting in coupling the arylides of the general formula in which R1 stands for the radical of a l-phenyl- 5-pyrazolone carboxylic acid, and in which R2 ll H HO wherein :0 stands for hydrogen or a substituent of the group consisting of CH3, OCI-Is and OC2H5, with unsulfonated aromatic diam-compounds.

9. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula /N= C 0 Ha l oo=H2 wherein m stands for hydrogen or a substituent of the group consisting of CH3, 001-13 and OCzI-Is, with sulfonated aromatic diazo-compounds.

10. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula stands for the radical of such an aromatic amine which contains two aromatic nuclei bound towherein m stands for hydrogen or a substituent of the group consisting of CH3, OCH3 and OCzHs,

with such sulfonated aromatic diazo-compounds whose o-position to the diazo-group is substituted by a substituent of the group comprising hydroxyl and carboxyl.

11. Process for the manufacture of azo-dyestuffs, consisting in coupling the arylides of the general formula 13. Process .for the manufacture of azo-dyestufis, consisting in coupling the arylides of the general formula N=CONH Rz l wherein R2 stands for the radical of such an aromatic amine which contains two aromatic nuclei linked by a connecting member, withunsulfonated aromatic diazo-compounds.

14. *Process for the manufacture of azo-dyestuffs, consisting in couplingthe arylide of the formula with unsulfonated aromatic diazo-compounds.

'15. Process for the manufacture of an azodyestufi, consisting in coupling the arylide of the formula with 2-diazo-4-chloro-1 1 '--diphenylether.

16. The azo-dyestufls characterized by the general formula wherein R3 represents the aromatic radical of any diazo-compouncl, RlCO represents the acyl radical of a carboxylic acid whose carboxyl group is directly linked to a cyclic nucleus, and whose capacity of coupling with diazo-compounds to produce azo-dyestuiis is due to the presence of H;/ I I H o ra -Q r5; 0 o H H wherein :1: stands for hydrogen or a substituent a CH2CO group, and R2 the radical of a poly- 9 of the group consisting of CH3, OCHs and OCzI-Is, cyclic aromatic amine, which products in a dry 0 with a sulfonated Z-diazo-l-benzene carboxylic state constitute yellow to orange to brown to red acid. powders which dissolve in solvents of the group 12. Process for the manufacture of azo-dyecomprising water and organic solvents to yellow stuifs, consisting in coupling the arylides of the to orangeto brown to red solutions. general formula CH3-C=N\ /N=CGH; x z I -H2=oo I l I l oo=rn l tWGOi? l 0 H H wherein :1: stands for hydrogen or a substituent 17. The pyrazolone azo-dyestuffs characterized of the group consisting of CH3, OCI-Is and OC2H5, by the general formula with the 5-sulfo-2-diazo-l-benzenecarboxylic m5 acid. R3N=NRiCONH-R2 wherein R3 represents the aromatic radical of any diazo-compound, R1 the radical of a 5-pyrazolone carboxylic acid, and R2 the radical of a polycyclic aromatic amine, which products in a dry state constitute. yellow to orange to brown to red powders which dissolve in solvents of the group comprising water and organic solvents to yellow to orange to brown to red-solutions.

18. The pyrazolone azo-dyestuifs characterized by the general formula wherein R3 represents. the aromatic radical of 2 any diazo-compound, R1 the radical of a 5-pywherein R3 represents the aromatic radical of any diazo-cornpound, R1 the radical of a 1- phenyl-5-pyrazolone carboxylic acid, and R2 the radical of such an aromatic amine which contains two aromatic nuclei bound together by a linkage, which products in a dry state constitute yellow to orange to brown to red powders which dissolve insolvent-s of the group comprising water and organic solvents to yellow to orange to brown to red solutions.

20. The pyrazolone azo-dyestuffs characterized by the general formula wherein R3 represents the aromatic radical of any diazo-compound, R1 the radical of a 1- I50 phenyl 5- pyrazolone carboxylic acid whose COOH-group is in the phenyl nucleus, and R2 the radical of such an aromatic amine which contains two aromatic nuclei bound together by a HI OH linkage, which products in a dry state constitute yellow to orange to brown to red powders which dissolve in solventsof the group comprising water and organic solvents to yellow to orange to brown tored solutions.

r 21. The pyrazolone azo-dyestuffs characterized by the general formula tints whichare characterized by their very good properties of fastness'.

24. The pyrazolone azo-dyestuifs characterized by the general formula II N l H o 0 wherein R represents the aromatic radical of any diazo-compound, wherein further a: stands for hydrogen or a substituent of the group consisting of CH3, OCH; and OC2H5, which products by the general formula H HO when dry constitute yellow to orange to brown to red powders which dissolve in solvents of the dissolve in water to yellow to orange to brown to red solutions, dyeing textiles yellow to orange to brown to red tints which are characterized by their very good properties of fastness.

25. The pyralzolone azo-dyestuffs characterized by the general formula group comprising water and organic solvents to yellow to orange to brown to red solutions.

22. The pyrazolone azo-dyestuffs characterized by the general formula wherein R represents the aromatic radical of a lcarboxyl-Z-diazobenzenesulfonic acid, wherein further :0 stands for hydrogen or a substituent of the group consisting of CH3, OCH: and OCzI-Is,

I ll a wherein R represents the aromatic radical of any diazo-compound, wherein further a: stands for hydrogen or a substituent of the group consisting of CH3, OCH; and OC2H5, which products when dry constitute yellow to orange to brown to red powders which dissolve in solvents of the group comprising water and organic solvents to yellow to orange to brown to red solutions.

23. The pyrazolone azo-dyestuffs characterized wherein R represents the aromatic radical of an unsulfonated diam-compound, wherein further a:

stands for hydrogen or a substituent of the group consisting of CH3, OCH: and OCzI-Is, which products when dry constitute yellow to orange to DIOWIl to red powders which dissolve in water to yellow to orange to brown to red solutions, dyeing textiles yellow to orange to brown to red.

which products when dry constitute yellow to orange to brown to red powders which dissolve in water to yellow to orange to brown to red solutions, dyeing textiles yellow to orange to brown to red tints which are characterized by their very good properties of fastness.

26. The pyrazolone azo-dyestufis characterized by the general formula wherein R represents the aromatic radical of the carboxyl-Zdiazobenzene-4-sulfonic acid, wherein further :c stands for hydrogen or a substituent of the group consisting of CH3, OCHs and OCzHs, which products when dry constitute yellow to orange to brown to red powders which dissolve in water to yellow to orange to brown to red solutions, dyeing textiles yellow to orange to brown to red tints which are characterized by their very good properties of fastness.

27. The pyrazolone azo-dyestuffscharacterized by the general formula 28. The pyrazolone azo-dyestufi of the formula Cl u i 'N=o-oN OK i 0 oil Ha which in a dry state constitutes an orange powder, dissolves in organic solvents to a yellow solution, and when produced on wool dyes the same fast reddish yellow tints.

GERALD BONHGTE. MAX SCHMID. 

